Metallic soap-resin solutions



Patented Apr. 24, W45

mid t METALLIC SUM-RESIN SGLU'IIEGNS Ralph E. Madison, Detroit, Mich, assignor to 'E'ruscon Laboratories, Inc, a corporation of Michigan No Drawing. Application July 11, 1942, Serial No. 458M533 (ca. zoo-is) 8 @laims.

This invention relates to stable metallic soap- I resin solutions and the method of manufacturing the same.

Heretofore, metallic soap-resin solutions have been prepared by grinding aluminum stearate or some other metallic scalp of the class which gels in the presence of a hydrocarbon solvent and a solvent in a pebble mill or the like and then adding the ground stearate to a resin solution. These metallic soap-resin solutions, so called, are not in fact solutions but aremerely suspensions of metallic soap in the resin solution. Microscopic examination revealed that in such socalled metallic soap-resin solutions contain relatively coarse metallic soap particles which formed or gathered into clumps rather than be uniformly dispersed throughout the so-called solution.

It has been discovered that certain of the metallic soap-resin solutions; preferably aluminum stearate-resin solutions, would produce extremely efiective curing compounds for use over freshly laid concrete to prevent loss of moisture therefrom during the setting or hydration of the cementitious structure. In the prior art, solutions of asphalt, paper, burlap and other coverings have been employed over freshly laid concrete, all with the primary object of preventing loss of moisture therefrom after the concrete is laid whereby to make all the moisture present in the concrete available to produce complete hydration of the cement therein. The asphalt solutions were unsightly and the paper, burlap and like covering were found to be too expensive.

The said prior art aluminum stearate-resin socalled solutions are so unstable and so lack sufficient fineness and uniformity of dispersion of the stearate particles as to be relatively inefiective to provide a continuous moisture retaining film over freshly laid concrete or the like, the film produced thereby being characterized by permitting a relatively high degree of evaporation of moisture therethrough from the freshly laid concrete or other cementitious structure therebelow.

Inasmuch as the prime value of curing compounds for freshly laid concrete or other sementitious structures is the retention of as much It should be noted that the instant invention differs from the invention disclosed and claimed in application for patent, Serial No. 450,634, filed July 11, 1942, for improvements in Stable non- .viscous metallic soap solutions in that gelling of the metallic soap is prevented in the instant case and is permitted in the case referred to. Various degrees of compatibility exist between different metallic soaps of the class which normally gel in the presence of a hydrocarbon solvent and various substantially unsaponifiable resins. The metallic soap particles in solutions manufactured in accordance with the case referred to will separate out of certain metallic soap-resin solutions manufactured therewith. However, stable metallic soap-resin solutions manufactured in accordance with the invention disclosed and claimed in this case will be completely stable on long standing. It was discovered that the preventing of gelling oi the metallic soap. in its hydrocarbon solvent by forming the slurry thereof as disclosed herein and then mixing the said treated slurry into the resin-solvent solution, a stable metallic soap-resin solution is obtained which is not only stable but is superior to prior art so-called metallic soap-resin solutions produced by means of grinding the metallic soap into a resin solution when used as a curing compound for-freshly laid cementitious structures.

To illustrate the invention, a single example of a stable aluminum stearate-resin solution embodying the invention and the particular method employed toproduce the same will be given, it being understood that a wide range of the proportions of the ingredients may be employed according to the type of metallic soap and resin selected, the example being given as illustrative of the invention and it is not intended to be lim-' iting in any sense.

ILLusrRA'rIvE EXAMPLE An electrolyte selected from the class of electrolytes consisting of concentrated hydrochloric acid, dilute nitric acid, and

An aluminum stearate slurry is first prepared by mixing the aluminum stearate with the hydrocarbon V. M. P. naphtha in a steam jacketed kettle equipped with anagitator. After uniformly mixing the aluminum stearate and the V. M. P. naphtha, steam is introduced into the jacketand the temperature of the mixture is raised. Before the temperature of the aluminum stearate-naphtha mixture rises above '75 to 100 degrees F., the butanol is added and mixed thoroughly with continuous agitation. The electrolyte is then added and mixed in thoroughly. The temperature of the slurry is then brought to a temperature preferably between 140 to 180 F., usually150 F. At this point, no thickening is observed,'the action of the butanol and hydrochloric acid on the alu minum stearate-naphtha mixture having prevented the expected thickening or gelling and having caused dispersion of the metallic soap particles. This solution or slurry is not transparent but is slightly cloudy or opalescent.

A resin solution is prepared previously to or simultaneously with the slurry in a separate tank by mixing at room temperature under continuous agitation the cumar resin preferably having a melting point of approximately 100 F., the coaltar naphtha, and the second item of V. M. P. naphtha. 7

When the slurry and resin solutions have been efl'ected, the .stearate solution from the steam kettle, preferably at 150 F., is slowly mixed with the resin solution, all under continuous and thor-' ough agitation.

The resulting solution is a stable aluminum tially uniform dispersion of the aluminum stearate throughout the solution and by the solution forming a substantially continuous and highly effective film when used as a curing compound over freshly laid concrete or other cementitious structures. As compared to earlier so-called aluminum stearate-resin solutions and other prior art, metallic soap-resin solutions embodying the invention show a very wide distribution 'or dispersion of the aluminum particles viewed as a substantially continuous cloudy effect. Substantially no clumping of the metallic soap particles can be observed, and the said metallic soap particles will be so small as to be diflicult to discern.

Thebutanol is not a solvent for the aluminum stearate, and is employed in the instant invention as a partial gel inhibitor. The electrolyte apparently acts in combination with the butanol as a total gel inhibitor and as a peptizer or polarizer, and, in combination with the butanol' entirely prevents the normal gelation of the metallic soap. Therefore, by employing the instant invention, metallic soap-resin solutions can be produced which. have uniform dispersion and compatibility of the metallic soap to such an extent that the solutions are more efflcient and effective as curing compounds than those of the prior art.

It is to be understood that theinvention is not limited to the precise formulae and ingredients given for illustrative purposes herein, and that any desired. hydrocarbon solvent known in the art such as mineral spirits, coal tar solvents,

'V. M. P. naphtha, xylene, turpentine, or the like 'and mixtures of the same may be employed as a carrier and solvent for the aluminum stearate and'resin in place of the V. M. P. naphtha, coal tar naphtha, and mineral spirits called for in the illustrative formulae given.

Although aluminum stearate is theonly metallic. soap referred to above, any and all of the aluminum or otherv metallic soaps which norstearate-resin solution characterized by substanrim of pan.)

mally gel in the presence of hydrocarbon solvents. Although butanol is the only alcohol referred to above, it is understood that other saturated aliphatic monohydric alcohols including and below amyl alcohol, such as ethyl, propyl, and butyl alcoholsjand their respective isomers, or any mixture thereof, may be employed in place thereof.

The term electrolyte as herein employed is intended to include concentrated hydrochloric .acid, dilute nitric acid, and concentrated aqua ammonia.

The term resin as herein employed is intended to include any and all resins of that class of unsaponifiable' resins which include cumar resins, terpene resins, paracournaroneindene resins, phenol-formaldehyde resins, terpene phenolic resins, and other substantially unsaponifiable resins having a saponification number of 25 or less.

Because of the fact that aluminum stearates and other metallic soaps which normally gel in the presence of hydrocarbon solvents vary in their characteristics, solvents from 2 to 25 times the weight of the metallic soap may be employed to obtain stable uniformly dispersed solutions by treatment with the alcohol-electrolyte method herein disclosed suitable for mixing with resin solutions to produce the ultimate eiiective metallic soap-resin solutions usable for curing compounds and the like.

The acid-electrolyte ratio varies widely with the types of stearates and solvents, such variation may run from 15% to of the acid by weight of the metallic soap and from 1% to 5% of the electrolyte by weight of the metallic soap.

Tests have proven that stable aluminum stearate-resin solutions and other metallic soap-resin solutions of the class described prepared in accordance with the invention used as curing-compounds for concrete orother cementitious structures have a much higher water retention ability than the so-called metallic soap-resin solutions manufactured under the conventional prior art grinding process. Following is a brief description of the method used to determine relative water retention efliciency of the stable metallic soap-resin solutions and conventional prior art stearate-resin solutions.

WATER RETENTION TEST Procedure Mixed concrete mortar (1 part cement to 1.85 parts of sand and suflicient water to form workable mixture) was placed in small tared pans (pie pans approximately six inches in diameter and A," deep), leveled oiT even with top of pan and weighed; After mortar had set sufficiently to resist abrasion from a small camel's hair brush (approximately two hours), pans were weighed,

and an amount of curing compound equivalent to a coverage of 200 square feet per gallon was measured onto the surfacewith a pipette and immediately brushed over entire surface, including rim of pan. (Calculated area covered includes Pans were immediately placed in oven maintained at F. and vented for circulation of fresh air. Pans were weighed at stated intervals. Loss of Water was calculated on the amount of water in mortar at time of application of curing compound. (Solids in curing compound are taken into consideration when percentage of water retention calculations are made.)

' ash-2,446

' vent and a hydrocarbon solvent, adding to said From the results of the above and other tests,

it can be and has been readily observed that considerably more water is retained in the concrete with aluminum stearate-resin solutions and other metallic soap-resin solutions produced in accordance with, the invention than with the curing compounds in which the stearate or metallic soap. and resin are ground. The water retention qualities of aluminum stearate-resin solutions and metallic soap-resin solutions made with various stearates with various hydrocarbon solvents, and with various unsaponiflable or substantially unsaponifiable hydrocarbon resins and the like in accordance with the alcohol-electrolyte treatment embodying the invention have been checked many times, and, inall cases the resulting more stable solution and more uniform distribution or dispersion of thealuminurn stearate or metallic soap particles has always resulted in a more efficient curing compound. By employing metallic soap-resin solutions produced in accordance with the invention and method steps disclosed, the maximum stability 'anddistribution or dispersion of the metallic soap particles is obtained, thus allowing for the maximum surface area of the metallic soap particles to be exposed with the consequent greater water-repellancy per unit weight of the metallic soap.

Although the chemical theory upon which the instant improvements inmetallic soap-resin solutions is not known and can only be surmised, the applicant has discovered that, by preventing the gelling of the metallic soap in its solvent, an extremely high degreeof compatibility of the metallic soap in the ultimate metallic soap-resin solution is accomplished, which compatibility no slurry while under-agitation a gelation inhibitor comprising a. saturated aliphatic mononvdric alcohol no higher in the class than amyl alcohol followed by a peptizing'agent comprising an acid selected from the class consisting of concentrated hydrochloric acid anddilute nitric acid, raising thetemperature oi the p ptized slurry to approximately 140 to 180 F. while maintaining agitation, removing the source of heat from said slurry, and slowlyand thoroughly mixing the said heated slurry into a solution of a unsaponiflable, synthetic resin and a solvent compatible with said resin and the metallic soap solvent.

2. The method of manufacturing stable solutions of the class described comprising the steps of iorming'a slurry of a metallic soap which normallygels in the presence of a hydrocarbon solvent and a hydrocarbon solvent, adding to said slurry while under a agitation of a gelation inhibitor comprising suficient saturated alian acidselected from the" class consisting f coni centrated hydrochloric acid and dilu nitric acid, raising the temperature of the ptized slurry'to approximately 140 to 180, while I doubt provides the maximum stability and dis tribution or dispersion oi the metallicsoap particles in the ultimate solution. By'accomplishing maximum distribution and stability metallic soap particles in metallic soap-resin solutions, such solutions function in a superior manner to the so-called prior art ground metallic soap-resin solutions when used as curing compounds for cementitious structures such as concrete and the like. 1 I

Although but one illustrative example ofthe invention and a single exposition of the method steps employed to produce improved and stable metallic soap-resin solutions embodying the instood that the invention herein shall be. deemed that defined by the appended claims construed vention have been'gi'ven herein, it is to be under -weight of the said metallic maintaining agitation, removing thesource of heat from said slurry, and slowly and thoroughly mixing the said heated slurry into a solution of a unsaponifiable, synthetic resin and a, solvent v compatible with said resin and the metallic soap solvent.

3. The method ofmanufacturing stable solutions of the class described comprising the steps of forming a slurry 'of a metallic soap which normally gels in the presence of a hydrocarbon solvent and a hydrocarbon solvent, adding to saidslurry while under agitation a gelation inhibitor comprising suflicient saturated aliphatic monohydric alcohol higher in the class than amyl alcohol'by weight of the metallic soap to prevent gelling of the said slurry. and 1% to 5% of an acid selected from the class consisting of concentrated hydrochloric acid and dilute nitric acid by'weight of the 'said metallic soap, raising the temperature of the peptized slurry toapp'roximately-l40f to 180 F. while maintaining agitation, removing the source of heat from .said

slurry, and slowly and thoroughly mixing the said heated slurry into a solution of a unsa-.,

ponifiable, synthetic hydrocarbon resin and a solvent compatible with said resin and the metallic soap solvent.

4. The method of manufacturing stable solutions of the class described comprising the steps of forming a slurry of ,a'metallic soap which normally gels in the presence of a hydrocarbon solvent and a hydrocarbon solvent, adding to said slurry while under agitation a gelation inhibitor comprising approximately 10% to 100% of saturated aliphatic 'monohydric alcohol no I higher-in the class than amyl alcohol by weight of the metallic soap and 1% to 5% of an acid selected from the class consisting of concentrated hydrochloric acid and dilute nitric acid by soap, raising the temperature of the peptized slurry to approximately to F. while maintaining agitation, removing the source of heat from said slurry, -and slowly and thoroughly mixing the .said heated slurry into a solution of a unsaponiflable, synthetichydrocarbdnresin and a solvent compatible with said resin and the metallic soap solvent.

5. A stable solution of the class described comprising a metallic soap having the characteristic of being capable of jelling in the presence of a hydrocarbon solvent, a hydrocarbon solvent in which said metallic soap is dissolved, and a saturated, aliphatic monohydric alcohol no higher in {the class than amyl alcohol, said alcohol being present in quantities insufiicient to prevent dispersion of said metallic soap in said solvent and as so limited being insufiicient' to reduce the solution to the desired fluidity, an acid selected from the class consisting of concentrated hydrochloric acid and dilute nitric acid in quantities adequate in combination with said alcohol to prevent gelling and to reduce the solution to said desired fluidity, and an unsaponifiable, synthetic resin in solution in a solvent compatible with said resin and the metallic soap solution.

6. A stable solution of the class described comprising a' metallic soap haying the characteristic of being capable of jelling in the presence of a hydrocarbon solvent, a hydrocarbon solvent in which said 'metallic soap is dissolved, and a saturated; aliphatic monohydric alcohol -no higher in the class than amyl alcohol in quantities in excess ofabout 10% by weightof said metallic soap but in quantities insufilcient to prevent dispersion of said metallic soap in said solvent and as so limited being insufficient to reduce the solution to the desired fluidity, an acid selected from the class consisting of concentrated hydrochloric acid and dilute nitric acid in quantities adequate in combination with said alcohol to prevent gelling and to reduce the solution, to said desired fluidity, and an unsaponifiable, synthetic resin in solution in a solvent compatible with said resin and the metallic soap solution.

7. A stable solution of the class described comprising a metallic soap having the characteristic of being capable of jelling in the presence of a hydrocarbon solvent, a hydrocarbon solvent in which said metallic soap is dissolved, a saturated, aliphatic monohydric alcohol no higher in the class than amyl alcohol, said alcohol being present in quantities insufficient to prevent dispersion of said metallic soap in said solvent and as so limited being insuflicient to reduce the solution to the desired fluidity, an acid selected from the class consisting .of concentrated hydrochloric acid and a dilute nitric acid in quantities in excess of about 1% of the weight of said metallic soap, said acid being adequate in combination with said alcohol to prevent gelling and to reduce the solution to said desired fluidity, and anunsaponifiable, synthetic resin in solution in a solvent compatible with said resin and the metallic soap solution.

8. A stable solution of the class described comprising a metallic soap having the characteristic of being capable of jelling in the presence of a hydrocarbon solvent, a-hydrocarbon solvent in which said metallic soap is dissolved, a saturated, aliphatic monohydric alcohol no higher. in the class than amyl alcohol, said alcohol being present in quantities insufllcient to prevent dispersion of said metallic soap in said solvent and as so limited being insuilicient to re'duce'the solu tion to the desired fluidity, an acid selected from the class consisting of concentrated hydrochloric acid and dilute nitric acid in quantities adequate in combination with said alcohol to prevent gelling and to reduce the solution to said desired fluidity, and an unsaponifiable, synthetic resin in solution in a solvent compatible with said resin and the metallic soap solution, said resin being present in amounts about thirty times by weight of said metallic soap.

RALPH E. MADISON.

all, 

